CN104475757A - Method for preparing nickel particles of special morphology - Google Patents
Method for preparing nickel particles of special morphology Download PDFInfo
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- CN104475757A CN104475757A CN201510005804.5A CN201510005804A CN104475757A CN 104475757 A CN104475757 A CN 104475757A CN 201510005804 A CN201510005804 A CN 201510005804A CN 104475757 A CN104475757 A CN 104475757A
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- hydrazine hydrate
- nickel
- polyvinylpyrrolidone
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Abstract
The invention discloses a method for preparing nickel particles of the special morphology and belongs to the field of metal materials. The method is characterized in that the amount of polyvinylpyrrolidone serving as a surface active agent and added to an ethanediol system and the concentration of a reactant are controlled so that the morphology of the nickel particles can be controlled. The process includes the steps that nickel chloride and polyvinylpyrrolidone are dissolved in ethanediol under the condition of strong stirring operation, after the nickel chloride and the polyvinylpyrrolidone are completely dissolved, hydrazine hydrate is added, blue emulsion is formed, stirred for a certain period and heated and then flows back, the particles obtained through back flow are centrifugally separated and washed through ethyl alcohol, and therefore a product is obtained. According to the method for preparing the nickel particles of the special morphology, the technology is simple, operation steps are fewer, no pressure equipment is needed, the process is safe and reliable, raw materials are low in cost and easy to obtain, the target product is pure, and no harmful impurities are generated. The nickel particles produced through the method are of a nano-particle-shaped structure with smooth surfaces or of a pinecone-shaped structure formed by assembling nano-particles or of a submicron spherical structure with the smooth surfaces or of a chained structure formed by assembling the particles. The nickel particles have the advantages of being even in particle diameter, large in specific area, high in anti-oxidization capacity and capable of meeting the requirements of various applications.
Description
Technical field: the preparation method that the present invention relates to a kind of special appearance nickel particle, belongs to metal material field.
Background technology: when the size of particle is reduced to sub-micron, nanoscale scope, the shape of particle also becomes extremely important, can be controlled the performance of material, obtain the material that performance is more superior by the size and pattern controlling particle.Then magnetic property and antioxygenic property can be improved to the control of magnetic Nano and sub-micron nickel granule-morphology, change electromagnetic performance and the catalytic performance of material, therefore, the nano nickle granules of various pattern was successively produced out in recent years, and the technology of preparing of special appearance nickel particle obtains and develops rapidly.The moderate monodispersed nickel granular powder of narrow size distribution, particle also has broad application prospects in fields such as military affairs and Aero-Space.The method that current preparation has the nickel particle of specific morphology mainly contains physicomechanical processes, electroless plating method, high-temperature hydrogen reduction method, hydro-thermal method, microemulsion method etc.Physical mechanical ball-milling method prepares that powder granule pattern is uneven, size is comparatively large, domain size distribution is wider; In chemical plating process, the impurity element such as phosphorus and boron can be introduced; High-temperature hydrogen reduction method needs high moderate pressure, and unreacted hydrogen has the hidden danger that set off an explosion, and is unfavorable for safety in production; Hydro-thermal method needs high-pressure installation; Microemulsion method is difficult to large-scale production.
Summary of the invention: the object of the invention is to provide a kind of preparation method of nickel particle of special appearance, by adjusting process parameter, realize nickel granule-morphology controlled synthesis, and prepared nickel granule-morphology is homogeneous, even particle size distribution, the nickel particle of special appearance has different magnetic properties and catalytic performance.Technical scheme of the present invention is: 1) by NiCl
26H
2o and polyvinylpyrrolidone ((C6H9NO)
n) put into ethylene glycol (HOCH
2cH
2oH), in, stir until the two dissolves completely, polyvinylpyrrolidone ((C6H9NO)
n) molecular weight be 8000g mol
-1-40000g mol
-1, NiCl
26H
2o and polyvinylpyrrolidone are at ethylene glycol (HOCH
2cH
2oH) concentration in is respectively 5-20mg/mL and 0-30mg/mL; 2) by volume fraction be 40%-80% hydrazine hydrate (N
2h
4h
2o) aqueous solution dropwise joins step 1 at 15-35 DEG C) in the solution prepared, the concentration of hydrazine hydrate in ethylene glycol is 0.01-0.1mL/mL, the process that drips with stirring, hydrazine hydrate (N
2h
4h
2o) aqueous solution stirs 5-30min after dripping again; 3) by step 2) mixed system of gained is heated to system boiling, and backflow, control return time is 5-90min, and the chemical reaction that this process works mainly comprises: N
2h
4+ 2H
2o+2e
-→ 2NH
3+ 2OH
-(1); N
2h
4+ 4OH
--4e
-→ N
2+ 4H
2o (2); Ni
2++ 2e
-→ Ni (3); In hydrazine hydrate heating process occur reduction such as formula (1) Suo Shi and oxidation reaction such as formula shown in (2), nickel ion occurs, such as formula the reduction reaction shown in (3), to obtain target product nickel under the reduction of hydrazine hydrate; 4) by step 3) reacted mixed system puts into rapidly ice-water bath cooling, and after solution cooling, rotating speed is that 2200-4000 rev/min of centrifugation is separated and obtains black powder, and washed 3-5 time by black powder with ethanol, drying at room temperature obtains final nickel particle.
The method that current preparation has the nickel particle of specific morphology mainly contains hydrazine hydrate reduction method etc. in physicomechanical processes, high-temperature hydrogen reduction method, hydro-thermal method, microemulsion method, polyol process, the aqueous solution.Physical mechanical ball-milling method prepares that powder granule pattern is uneven, size is comparatively large, domain size distribution is wider; High-temperature hydrogen reduction method needs high moderate pressure, and unreacted hydrogen has the hidden danger that set off an explosion, and is unfavorable for safety in production; Hydro-thermal method needs high-pressure installation; Microemulsion method is difficult to large-scale production, and polyol process needs to add the nucleators such as precious metals pd, and in the aqueous solution, hydrazine hydrate reduction method needs to add NaOH, regulates pattern by regulating pH or temperature.Adopt ethylene glycol to be solvent in the present invention, there is not oxide or hydroxide in nickel product, at system reflux course, hydrazine hydrate, except as reducing agent, also can provide OH
-, guarantee system does not need to add NaOH, would not there is Na like this in later stage cleaning process
+, cleaning process is simple, ensures that reaction is carried out smoothly.Preparation method's technique of the present invention is simple, does not need press device, and process safety is reliable, controls nickel granule-morphology by controlling to add material concentration.In addition, the method cheaper starting materials is easy to get, and accessory substance is nitrogen, without strong alkaline substances such as NaOH in process, does not produce objectionable impurities.Compared to Existing methods, it is simple that the inventive method has process, and without objectionable impurities product, target product particle diameter, pattern, purity, surface nature are easy to the feature controlled.The structures such as the nickel particle adopting the inventive method to prepare is ganoid Nanoparticulate, the pinecone shape assembled by nano particle, ganoid sub-micron chain that is spherical, that assembled by spherical particle, it has the advantages that grain diameter is even, specific area is large, anti-aging capability is strong, and the nickel particle performance of special appearance has gone out different magnetic properties, therefore, the nickel particle of these special appearances can be applied to magnetic material, catalyst, battery, the aspect such as anticorrosion.
Accompanying drawing illustrates:
Fig. 1 is the scanning electron microscope (SEM) photograph of gained nickel particle in detailed description of the invention 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of gained nickel particle in detailed description of the invention 2;
Fig. 3 is the scanning electron microscope (SEM) photograph of gained nickel particle in detailed description of the invention 3;
Fig. 4 is the scanning electron microscope (SEM) photograph of gained nickel particle in detailed description of the invention 4;
In Fig. 5, a, b, c, d are respectively the X-ray diffraction spectrogram of detailed description of the invention 1,2,3 and 4 gained nickel particle;
In Fig. 6, a, b, c, d are respectively the hysteresis curve of detailed description of the invention 1,2,3 and 4 gained nickel particle.
Fig. 7 is the scanning electron microscope (SEM) photograph of gained nickel particle in detailed description of the invention 5;
Fig. 8 is the scanning electron microscope (SEM) photograph of gained nickel particle in detailed description of the invention 6;
Fig. 9 is the scanning electron microscope (SEM) photograph of gained nickel particle in detailed description of the invention 7;
Figure 10 is the scanning electron microscope (SEM) photograph of gained nickel particle in detailed description of the invention 8;
Figure 11 is the scanning electron microscope (SEM) photograph of gained nickel particle in detailed description of the invention 9;
Figure 12 is the scanning electron microscope (SEM) photograph of gained nickel particle in detailed description of the invention 10;
Detailed description of the invention:
Embodiment 1: a kind of preparation method of nickel particle of special appearance carries out according to the following steps, one, the NiCl of certain mass that will weigh
26H
2o puts into ethylene glycol, strong stirring until dissolve completely, control NiCl
26H
2the concentration of O is 10.0mg/mL; Two, dropwise joined under the condition of room temperature strong stirring by the hydrazine hydrate measured in the solution that step one prepares, the concentration of hydrazine hydrate is stir 5-30min again after 0.05mL/mL drips hydrazine hydrate; Three, the mixed system of step 2 gained is heated to the boiling under reflux of system, control return time is 60min; Four, step 3 products obtained therefrom is put into rapidly ice-water bath cooling, after solution cooling, centrifugation obtains black powder, washed 3-5 time by black powder with ethanol, drying at room temperature obtains final nickel particle, and pattern as shown in Figure 1, polyvinylpyrrolidone is 0 in the concentration of system, the nano particle of uniform particle sizes, the crystalline phase composition of nano nickle granules is as shown in a in Fig. 5, and the hysteresis curve under the room temperature of nano nickle granules is as shown in a in Fig. 6;
Embodiment 2: a kind of preparation method of nickel particle of special appearance carries out according to the following steps, one, the NiCl of certain mass that will weigh
26H
2o and polyvinylpyrrolidone put into ethylene glycol, strong stirring until dissolve completely, control NiCl
26H
2the concentration of O is 5.0mg/mL, and the concentration of polyvinylpyrrolidone is 15mg/mL; Two, dropwise joined under the condition of room temperature strong stirring by the hydrazine hydrate measured in the solution that step one prepares, the concentration of hydrazine hydrate is stir 5-30min again after 0.025mL/mL drips hydrazine hydrate; Three, the mixed system of step 2 gained is heated to the boiling under reflux of system, control return time is 60min; Four, step 3 products obtained therefrom is put into rapidly ice-water bath cooling, after solution cooling, centrifugation obtains black powder, washed 3-5 time by black powder with ethanol, drying at room temperature obtains final nickel particle, and pattern as shown in Figure 2, adjust the concentration of each raw material, can obtain the pinecone shape nickel particle assembled by nano particle, the crystalline phase composition of nickel particle is as shown in the b in Fig. 5, and the hysteresis curve under the room temperature of pinecone shape nickel particle is as shown in the b in Fig. 6;
Embodiment 3: a kind of preparation method of nickel particle of special appearance carries out according to the following steps, one, the NiCl of certain mass that will weigh
26H
2o and polyvinylpyrrolidone put into ethylene glycol, strong stirring until dissolve completely, control NiCl
26H
2the concentration of O is 10.0mg/mL, and the concentration of polyvinylpyrrolidone is 15.0mg/mL; Two, dropwise joined under the condition of room temperature strong stirring by the hydrazine hydrate measured in the solution that step one prepares, the concentration of hydrazine hydrate is stir 5-30min again after 0.05mL/mL drips hydrazine hydrate; Three, the mixed system of step 2 gained is heated to the boiling under reflux of system, control return time is 5min; Four, step 3 products obtained therefrom is put into rapidly ice-water bath cooling, after solution cooling, centrifugation obtains black powder, with ethanol, black powder is washed 3-5 time, drying at room temperature obtains final nickel granule-morphology as shown in Figure 3, adjusts the concentration of each raw material, can obtain the spherical nickel particle of ganoid sub-micron, crystalline phase composition is as shown in the c in Fig. 5, and the hysteresis curve under the room temperature of the spherical nickel particle of sub-micron is as shown in the c in Fig. 6;
Embodiment 4: a kind of preparation method of nickel particle of special appearance carries out according to the following steps, one, the NiCl of certain mass that will weigh
26H
2o and polyvinylpyrrolidone put into ethylene glycol, strong stirring until dissolve completely, control NiCl
26H
2the concentration of O is 10.0mg/mL, and the concentration of polyvinylpyrrolidone is 15.0mg/mL; Two, dropwise joined under the condition of room temperature strong stirring by the hydrazine hydrate measured in the solution that step one prepares, the concentration of hydrazine hydrate is stir 5-30min again after 0.05mL/mL drips hydrazine hydrate; Three, the mixed system of step 2 gained is heated to the boiling under reflux of system, control return time is 60min; Four, step 3 products obtained therefrom is put into rapidly ice-water bath cooling, after solution cooling, centrifugation obtains black powder, with ethanol, black powder is washed 3-5 time, drying at room temperature obtains final nickel granule-morphology as shown in Figure 4, adjusts the concentration of each raw material, can obtain the chain shape nickel particle assembled by spherical particle, as fig 5d, the hysteresis curve under the room temperature of the spherical nickel particle of sub-micron is as shown in the d in Fig. 6 for crystalline phase composition; ;
Embodiment 5: a kind of preparation method of nickel particle of special appearance carries out according to the following steps, one, the NiCl of certain mass that will weigh
26H
2o and polyvinylpyrrolidone put into ethylene glycol, strong stirring until dissolve completely, control NiCl
26H
2the concentration of O is 10.0mg/mL, and the concentration of polyvinylpyrrolidone is 30.0mg/mL; Two, dropwise joined under the condition of room temperature strong stirring by the hydrazine hydrate measured in the solution that step one prepares, the concentration of hydrazine hydrate is stir 5-30min again after 0.05mL/mL drips hydrazine hydrate; Three, the mixed system of step 2 gained is heated to the boiling under reflux of system, control return time is 60min; Four, step 3 products obtained therefrom is put into rapidly ice-water bath cooling, after solution cooling, centrifugation obtains black powder, is washed 3-5 time by black powder with ethanol, and drying at room temperature obtains final nickel granule-morphology as shown in Figure 7;
Embodiment 6: a kind of preparation method of nickel particle of special appearance carries out according to the following steps, one, the NiCl of certain mass that will weigh
26H
2o and polyvinylpyrrolidone put into ethylene glycol, strong stirring until dissolve completely, control NiCl
26H
2the concentration of O is 10.0mg/mL, and the concentration of polyvinylpyrrolidone is 40.0mg/mL; Two, dropwise joined under the condition of room temperature strong stirring by the hydrazine hydrate measured in the solution that step one prepares, the concentration of hydrazine hydrate is stir 5-30min again after 0.05mL/mL drips hydrazine hydrate; Three, the mixed system of step 2 gained is heated to the boiling under reflux of system, control return time is 60min; Four, step 3 products obtained therefrom is put into rapidly ice-water bath cooling, after solution cooling, centrifugation obtains black powder, is washed 3-5 time by black powder with ethanol, and drying at room temperature obtains final nickel granule-morphology as shown in Figure 8;
Embodiment 7: a kind of preparation method of nickel particle of special appearance carries out according to the following steps, one, the NiCl of certain mass that will weigh
26H
2o and polyvinylpyrrolidone put into ethylene glycol, strong stirring until dissolve completely, control NiCl
26H
2the concentration of O is 20.0mg/mL, and the concentration of polyvinylpyrrolidone is 15.0mg/mL; Two, dropwise joined under the condition of room temperature strong stirring by the hydrazine hydrate measured in the solution that step one prepares, the concentration of hydrazine hydrate is stir 5-30min again after 0.05mL/mL drips hydrazine hydrate; Three, the mixed system of step 2 gained is heated to the boiling under reflux of system, control return time is 60min; Four, step 3 products obtained therefrom is put into rapidly ice-water bath cooling, after solution cooling, centrifugation obtains black powder, is washed 3-5 time by black powder with ethanol, and drying at room temperature obtains final nickel granule-morphology as shown in Figure 9;
Embodiment 8: a kind of preparation method of nickel particle of special appearance carries out according to the following steps, one, the NiCl of certain mass that will weigh
26H
2o and polyvinylpyrrolidone put into ethylene glycol, strong stirring until dissolve completely, control NiCl
26H
2the concentration of O is 20.0mg/mL, and the concentration of polyvinylpyrrolidone is 30.0mg/mL; Two, dropwise joined under the condition of room temperature strong stirring by the hydrazine hydrate measured in the solution that step one prepares, the concentration of hydrazine hydrate is stir 5-30min again after 0.05mL/mL drips hydrazine hydrate; Three, the mixed system of step 2 gained is heated to the boiling under reflux of system, control return time is 60min; Four, step 3 products obtained therefrom is put into rapidly ice-water bath cooling, after solution cooling, centrifugation obtains black powder, is washed 3-5 time by black powder with ethanol, and drying at room temperature obtains final nickel granule-morphology as shown in Figure 10;
Embodiment 9: a kind of preparation method of nickel particle of special appearance carries out according to the following steps, one, the NiCl of certain mass that will weigh
26H
2o and polyvinylpyrrolidone put into ethylene glycol, strong stirring until dissolve completely, control NiCl
26H
2the concentration of O is 10.0mg/mL, and the concentration of polyvinylpyrrolidone is 15.0mg/mL; Two, dropwise joined under the condition of room temperature strong stirring by the hydrazine hydrate measured in the solution that step one prepares, the concentration of hydrazine hydrate is stir 5-30min again after 0.05mL/mL drips hydrazine hydrate; Three, the mixed system of step 2 gained is heated to the boiling under reflux of system, control return time is 10min; Four, step 3 products obtained therefrom is put into rapidly ice-water bath cooling, after solution cooling, centrifugation obtains black powder, is washed 3-5 time by black powder with ethanol, and drying at room temperature obtains final nickel granule-morphology as shown in Figure 11;
Embodiment 10: a kind of preparation method of nickel particle of special appearance carries out according to the following steps, one, the NiCl of certain mass that will weigh
26H
2o and polyvinylpyrrolidone put into ethylene glycol, strong stirring until dissolve completely, control NiCl
26H
2the concentration of O is 10.0mg/mL, and the concentration of polyvinylpyrrolidone is 15.0mg/mL; Two, dropwise joined under the condition of room temperature strong stirring by the hydrazine hydrate measured in the solution that step one prepares, the concentration of hydrazine hydrate is stir 5-30min again after 0.05mL/mL drips hydrazine hydrate; Three, the mixed system of step 2 gained is heated to the boiling under reflux of system, control return time is 90min; Four, step 3 products obtained therefrom is put into rapidly ice-water bath cooling, after solution cooling, centrifugation obtains black powder, is washed 3-5 time by black powder with ethanol, and drying at room temperature obtains final nickel granule-morphology as shown in Figure 12.
Claims (1)
1. a preparation method for special appearance nickel particle, is characterized in that: comprise following process steps:
1) by NiCl
26H
2o and polyvinylpyrrolidone ((C6H9NO)
n) put into ethylene glycol (HOCH
2cH
2oH), in, stir until the two dissolves completely, polyvinylpyrrolidone ((C6H9NO)
n) molecular weight be 8000g mol
-1-40000g mol
-1, NiCl
26H
2o and polyvinylpyrrolidone are at ethylene glycol (HOCH
2cH
2oH) concentration in is respectively 5-20mg/mL and 0-30mg/mL;
2) by volume fraction be 40%-80% hydrazine hydrate (N
2h
4h
2o) aqueous solution dropwise joins step 1 at 15-35 DEG C) in the solution prepared, the concentration of hydrazine hydrate in ethylene glycol is 0.01-0.1mL/mL, the process that drips with stirring, hydrazine hydrate (N
2h
4h
2o) aqueous solution stirs 5-30min after dripping again;
3) by step 2) mixed system of gained is heated to system boiling, and backflow, control return time is 5-90min, and the chemical reaction that this process works mainly comprises: N
2h
4+ 2H
2o+2e
-→ 2NH
3+ 2OH
-(1); N
2h
4+ 4OH
--4e
-→ N
2+ 4H
2o (2); Ni
2++ 2e
-→ Ni (3); In hydrazine hydrate heating process occur reduction such as formula (1) Suo Shi and oxidation reaction such as formula shown in (2), nickel ion occurs, such as formula the reduction reaction shown in (3), to obtain target product nickel under the reduction of hydrazine hydrate;
4) by step 3) reacted mixed system puts into rapidly ice-water bath cooling, and after solution cooling, rotating speed is that 2200-4000 rev/min of centrifugation is separated and obtains black powder, and washed 3-5 time by black powder with ethanol, drying at room temperature obtains final nickel particle.
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|---|---|---|---|
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|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024250A (en) * | 2006-12-31 | 2007-08-29 | 中国科学技术大学 | Method formaking polycrystalline uniform nickel microball and line-shape nickel chain |
| CN101024251A (en) * | 2007-03-08 | 2007-08-29 | 西北工业大学 | Method for preparing nano metal |
| CN101417341A (en) * | 2008-11-07 | 2009-04-29 | 江苏科技大学 | Method for preparing metal nickel nano hollow bal |
| CN101486102A (en) * | 2009-01-05 | 2009-07-22 | 江苏科技大学 | Method for preparing metallic nickel nano-wire |
| US20110031001A1 (en) * | 2009-08-10 | 2011-02-10 | Hitachi Cable Ltd. | Composite metal fine particle material, metal film and manufacturing method of the metal film, and printed wiring board and cable |
-
2015
- 2015-01-07 CN CN201510005804.5A patent/CN104475757A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024250A (en) * | 2006-12-31 | 2007-08-29 | 中国科学技术大学 | Method formaking polycrystalline uniform nickel microball and line-shape nickel chain |
| CN101024251A (en) * | 2007-03-08 | 2007-08-29 | 西北工业大学 | Method for preparing nano metal |
| CN101417341A (en) * | 2008-11-07 | 2009-04-29 | 江苏科技大学 | Method for preparing metal nickel nano hollow bal |
| CN101486102A (en) * | 2009-01-05 | 2009-07-22 | 江苏科技大学 | Method for preparing metallic nickel nano-wire |
| US20110031001A1 (en) * | 2009-08-10 | 2011-02-10 | Hitachi Cable Ltd. | Composite metal fine particle material, metal film and manufacturing method of the metal film, and printed wiring board and cable |
Non-Patent Citations (1)
| Title |
|---|
| NING WANG ET AL: "Nickel Chains Assembled by Hollow Microspheres and Their Magnetic Properties", 《J. PHYS. CHEM. C》 * |
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Application publication date: 20150401 |